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WO2017081758A1 - Matériau actif d'électrode négative pour dispositif électrique, et dispositif électrique utilisant ledit matériau - Google Patents

Matériau actif d'électrode négative pour dispositif électrique, et dispositif électrique utilisant ledit matériau Download PDF

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Publication number
WO2017081758A1
WO2017081758A1 PCT/JP2015/081662 JP2015081662W WO2017081758A1 WO 2017081758 A1 WO2017081758 A1 WO 2017081758A1 JP 2015081662 W JP2015081662 W JP 2015081662W WO 2017081758 A1 WO2017081758 A1 WO 2017081758A1
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WIPO (PCT)
Prior art keywords
phase
active material
negative electrode
electrode active
silicide
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PCT/JP2015/081662
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English (en)
Japanese (ja)
Inventor
千葉　啓貴
洋一 吉岡
智裕 蕪木
渡邉　学
誠也 荒井
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Motor Co Ltd filed Critical Nissan Motor Co Ltd
Priority to MYPI2018000669A priority Critical patent/MY173412A/en
Priority to CN201580084375.3A priority patent/CN108352513B/zh
Priority to US15/774,920 priority patent/US10403890B2/en
Priority to KR1020187012641A priority patent/KR20180061348A/ko
Priority to EP15908282.5A priority patent/EP3376570B1/fr
Priority to PCT/JP2015/081662 priority patent/WO2017081758A1/fr
Priority to JP2017549910A priority patent/JP6583426B2/ja
Publication of WO2017081758A1 publication Critical patent/WO2017081758A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/06—Metal silicides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/048—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by pulverising a quenched ribbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode active material for an electric device and an electric device using the same.
  • the negative electrode active material for an electric device and the electric device using the same according to the present invention include, for example, a driving power source and an auxiliary power source for a motor of a vehicle such as an electric vehicle, a fuel cell vehicle, and a hybrid electric vehicle as a secondary battery or a capacitor Used for.
  • Motor drive secondary batteries are required to have extremely high output characteristics and high energy compared to consumer lithium ion secondary batteries used in mobile phones and notebook computers. Therefore, lithium ion secondary batteries having the highest theoretical energy among all the batteries are attracting attention, and are currently being developed rapidly.
  • a lithium ion secondary battery includes a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder, and a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder.
  • a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder
  • a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder.
  • it has the structure connected through an electrolyte layer and accommodated in a battery case.
  • a lithium ion secondary battery using a material that is alloyed with Li for the negative electrode has a large expansion and contraction in the negative electrode during charge and discharge.
  • the volume expansion is about 1.2 times in graphite materials
  • Si materials when Si and Li are alloyed, transition from the amorphous state to the crystalline state causes a large volume change. (Approximately 4 times), there was a problem of reducing the cycle life of the electrode.
  • the capacity and the cycle durability are in a trade-off relationship, and there is a problem that it is difficult to improve the cycle durability while exhibiting a high capacity.
  • Patent Document 1 discloses an invention that aims to provide a non-aqueous electrolyte secondary battery having a negative electrode pellet having a high capacity and an excellent cycle life.
  • a silicon-containing alloy obtained by mixing silicon powder and titanium powder by a mechanical alloying method and wet-pulverizing the first phase mainly composed of silicon and a silicide of titanium (such as TiSi 2 ) ) Containing a second phase containing) is disclosed as a negative electrode active material.
  • a silicon-containing alloy obtained by mixing silicon powder and titanium powder by a mechanical alloying method and wet-pulverizing the first phase mainly composed of silicon and a silicide of titanium (such as TiSi 2 ) ) Containing a second phase containing) is disclosed as a negative electrode active material.
  • at least one of these two phases is amorphous or low crystalline.
  • an object of the present invention is to provide means capable of improving cycle durability of an electric device such as a lithium ion secondary battery.
  • the present inventors have conducted intensive research to solve the above problems. As a result, it has a ternary alloy composition represented by Si-Sn-M (M is one or more transition metal elements), and its microstructure is a transition metal silicide (also referred to as silicide). ) As a main component (silicide phase) and a second phase (amorphous) containing Sn as a main component and amorphous or low crystalline silicon (also referred to as a-Si) as a main component Silicon having a Si phase (a-Si phase), a part of which is a plurality of independent first phases, and a part of which is a eutectic structure of the first phase and the second phase. The present inventors have found that the above problems can be solved by using a contained alloy as a negative electrode active material for an electric device, and have completed the present invention.
  • the present invention relates to a negative electrode active material for electric devices made of a silicon-containing alloy.
  • the silicon-containing alloy has the following chemical formula (1):
  • the silicon-containing alloy includes a first phase mainly composed of a transition metal silicide (silicide) as a main component and a part of Sn, and is mainly composed of amorphous or low crystalline Si. Characterized in that the first phase is a plurality of independent first phases, and that the first phase and the second phase are eutectic structures. Have.
  • the silicon-containing alloy constituting the negative electrode active material according to the present invention has a structure in which the second phase is eutectic with the first phase and further enters a plurality of independent first phase gaps in the microstructure. ing.
  • the first phase is superior in terms of hardness and electronic conductivity compared to the second phase (a-Si phase). Therefore, the expansion of the second phase (a-Si phase) in the eutectic structure during the charge / discharge process is suppressed by the eutectic first phase, and further, a plurality of independent first phases are suppressed. It can be suppressed by restraining the stance.
  • FIG. 1 is a schematic cross-sectional view schematically showing an outline of a laminated flat non-bipolar lithium ion secondary battery which is a typical embodiment of an electric device according to the present invention.
  • FIG. 1 is a perspective view schematically showing the appearance of a stacked flat lithium ion secondary battery that is a representative embodiment of an electric device according to the present invention.
  • FIG. 3A shows a BF (Bright-field) -STEM Image (bright-field-scanning transmission electron microscope image) (low magnification) of a sample prepared by FIB method for the silicon-containing alloy (particles) of this embodiment. It is a drawing.
  • FIG. 1 is a schematic cross-sectional view schematically showing an outline of a laminated flat non-bipolar lithium ion secondary battery which is a typical embodiment of an electric device according to the present invention.
  • FIG. 1 is a perspective view schematically showing the appearance of a stacked flat lithium ion secondary battery that is a representative embodiment of an electric
  • FIG. 3B is a drawing showing a HAADF-STEM Image (high angle scattering dark field-scanning transmission electron microscope image) of active material particles in the same field of view as FIG.
  • FIG. 4 is a drawing showing quantitative mapping data by STEM-EDX (scanning transmission electron microscope-energy dispersive X-ray spectroscopy).
  • FIG. 4 (a) is the same HAADF-STEM image as FIG. 3 (b).
  • FIG. 4B is a diagram showing mapping data of Sn (lower left) measured in the same field of view as HAADF-STEM (upper left FIG. 4A).
  • FIG. 4C is a diagram showing mapping data of Si (lower center) measured in the same field of view as HAADF-STEM (upper left FIG. 4A).
  • FIG. 4 is a drawing showing a HAADF-STEM Image (high angle scattering dark field-scanning transmission electron microscope image) of active material particles in the same field of view as FIG.
  • FIG. 4 is a drawing showing
  • FIG. 4D is a drawing showing mapping data of Ti (lower right) measured in the same field of view as HAADF-STEM (upper left FIG. 4A).
  • FIG. 4 (e) is a diagram (upper right) in which mapping data of Sn, Si, and Ti measured in the same field of view as HAADF-STEM (upper left FIG. 4 (a)).
  • FIG. 5A is a drawing (medium magnification) showing a BF (Bright-field) -STEM Image (bright-field-scanning transmission electron microscope image) in which the eutectic structure of the silicon-containing alloy (particles) of the present embodiment is enlarged. It is.
  • FIG. 5B is a drawing showing a HAADF-STEM Image (high angle scattering dark field-scanning transmission electron microscope image) of the active material particles in the same field of view as FIG.
  • FIG. 6A shows a BF (Bright-field) -STEM Image (bright field-scanning transmission electron microscope image) obtained by further enlarging a part of the eutectic structure of the silicon-containing alloy (particle) of this embodiment. It is a drawing (high magnification).
  • FIG. 6B is a drawing showing the HAADF-STEM Image (high angle scattering dark field-scanning transmission electron microscope image) of the active material particles in the same field of view as FIG. FIG.
  • FIG. 7 is a drawing showing quantitative mapping data by STEM-EDX (scanning transmission electron microscope-energy dispersive X-ray spectroscopy).
  • FIG. 7 (a) is the same HAADF-STEM image as FIG. 6 (b).
  • FIG. 7B is a drawing showing mapping data of Sn (lower left) measured in the same field of view as HAADF-STEM (upper left FIG. 7A).
  • FIG. 7C is a diagram showing mapping data of Si (lower center) measured in the same field of view as HAADF-STEM (upper left FIG. 7A).
  • FIG. 7D is a drawing showing mapping data of Ti (lower right) measured in the same field of view as HAADF-STEM (upper left FIG. 7A).
  • FIG. 7 is a drawing showing quantitative mapping data by STEM-EDX (scanning transmission electron microscope-energy dispersive X-ray spectroscopy).
  • FIG. 7 (a) is the same HAADF-STEM image as FIG. 6 (b).
  • FIG. 7E is a drawing (upper right) in which mapping data of Sn, Si, and Ti measured in the same field of view as HAADF-STEM (upper left FIG. 7A) are superimposed.
  • FIG. 8 is the same HAADF-STEM image as FIG. 6B and FIG. 7A, and the elements in the silicide phase (first phase) and the Si phase (second phase) by elemental analysis. This is a drawing in which the region (2 places surrounded by a square frame) for observing the presence of the element is divided into numbers 1-2 in the image.
  • FIG. 8 (a) is the same HAADF-STEM image as FIG. 6 (b) and FIG. 7 (a), and the rectangular frame of the portion to be observed for the element distribution (the portion of the circled number 1 in the image).
  • FIG. 9B is a drawing in which elemental analysis is performed on a portion to be observed of the element distribution of FIG. 9A.
  • FIG. 9C is an element analysis table summarizing the elemental analysis results of FIG. FIG. 10A shows the same HAADF-STEM Image (high angle scattering dark field-scanning transmission electron microscope image) as in FIG. 3B.
  • FIG. 10 (b) is an enlarged view of a part of the eutectic structure in the right-side enclosure in FIG. 10 (a), and the same HAADF-STEM Image (high angle scattering dark field as in FIG.
  • FIG. 10C is a diffraction pattern obtained by performing fast Fourier transform processing on an independent silicide phase region in the left enclosing portion of FIG. 10A by electron diffraction measurement.
  • FIG. 10D is a diffraction pattern obtained by subjecting the region of the a-Si phase in the eutectic structure of FIG. 10B to fast Fourier transform by electron diffraction measurement.
  • FIG. 10E is a diffraction pattern obtained by performing a fast Fourier transform process on the silicide phase region in the eutectic structure of FIG. 10B by electron diffraction measurement.
  • FIG. 10C is a diffraction pattern obtained by performing fast Fourier transform processing on an independent silicide phase region in the left enclosing portion of FIG. 10A by electron diffraction measurement.
  • FIG. 10D is a diffraction pattern obtained by subjecting the region of the a-Si phase in the eutectic structure of FIG. 10B to fast Fourier transform
  • FIG. 11 is a chart obtained by (powder) X-ray diffraction (XRD) measurement of the same alloy of Example 2 as FIG.
  • FIG. 12 shows a Si—Sn—Ti ternary equilibrium diagram when the Si—Sn—Ti ternary alloy temperature is 1400 ° C.
  • FIG. 13 shows a Si—Sn—Ti ternary equilibrium diagram when the temperature of the Si—Sn—Ti ternary alloy is 1450 ° C.
  • FIG. 14 shows a Si—Sn—Ti ternary equilibrium diagram when the temperature of the Si—Sn—Ti ternary alloy is 1300 ° C.
  • FIG. 15 shows an Si—Sn—Ti ternary equilibrium diagram when the temperature of the Si—Sn—Ti ternary alloy is 1200 ° C.
  • FIG. 16 is a diagram in which analysis information is included in the state diagram of FIG.
  • FIG. 17 is a drawing in which analysis information is included in a Si—Sn—Ti ternary equilibrium diagram at a Si—Sn—Ti ternary alloy temperature of 1310 ° C.
  • FIG. FIG. 18 shows a liquid phase projection view of the Si—Sn—Ti ternary system by Thermo-Calc (integrated thermodynamic calculation system).
  • FIG. 19 is a diagram showing a state in which the temperature of the quenched ribbon alloy obtained by the apparatus used in the liquid quenched roll solidification method is observed using an infrared thermograph.
  • FIG. 20 is a graph plotting the temperature of the quenched ribbon alloy at positions (distances) every 2.25 mm from the nozzle for Examples 2 and 4.
  • FIG. 21 shows the number of rotations of the roll and the cooling time of the quenched ribbon alloy (from 1450 ° C. to 1100 ° C.) in FIG. ) A graph showing the relationship with temperature.
  • FIG. 22 (a) shows the alloy composition of Si 65 Sn 5 Ti 30 of Example 1 and the size of the independent first phase obtained by the above precipitation calculation by applying the calculation conditions of Example 1 above.
  • FIG. 24B is a graph obtained by enlarging the graph of FIG. 24A and obtaining the radius distribution of the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure. is there.
  • FIG. 25 is a drawing showing a cross-sectional SEM (scanning electron microscope) image of the quenched ribbon alloy of Si 60 Sn 10 Ti 30 in Example 2.
  • FIG. 26A shows the alloy composition of Si 60 Sn 10 Ti 30 of Example 3 and the size of the independent first phase obtained by the above precipitation calculation by applying the calculation conditions of Example 3 above.
  • FIG. 28B is a graph obtained by enlarging the graph of FIG. 28A and obtaining the radius distribution of the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure. is there.
  • FIG. 29 is a drawing showing a cross-sectional SEM (scanning electron microscope) image of the quenched ribbon alloy of Si 60 Sn 10 Ti 30 of Example 4.
  • FIG. 30 (a) shows the silicide (first structure) in the eutectic structure obtained by the above precipitation calculation with respect to the alloy composition of Si 60 Sn 20 Ti 20 in Comparative Example 1 by applying the calculation conditions in Comparative Example 1 above.
  • a negative electrode for a lithium ion secondary battery which is a typical embodiment of a negative electrode including a negative electrode active material for an electric device according to the present invention, and a lithium ion secondary battery using the same
  • a cell (single cell layer) ) Voltage is large, and high energy density and high power density can be achieved. Therefore, the lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of the present embodiment is excellent as a vehicle driving power source or an auxiliary power source.
  • it can be suitably used as a lithium ion secondary battery for a vehicle driving power source or the like.
  • the present invention can be sufficiently applied to lithium ion secondary batteries for portable devices such as mobile phones.
  • the lithium ion secondary battery that is the subject of the present embodiment may be any one that uses the negative electrode active material for the lithium ion secondary battery of the present embodiment described below. It should not be restricted in particular.
  • a solution electrolyte type battery using a solution electrolyte such as a nonaqueous electrolyte solution for the electrolyte layer, a polymer battery using a polymer electrolyte for the electrolyte layer, etc. It can be applied to any conventionally known electrolyte layer type.
  • the polymer battery is further divided into a gel electrolyte type battery using a polymer gel electrolyte (also simply referred to as gel electrolyte) and a solid polymer (all solid) type battery using a polymer solid electrolyte (also simply referred to as polymer electrolyte). It is done.
  • the non-bipolar (internal parallel connection type) lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of this embodiment will be described very simply with reference to the drawings.
  • the technical scope of the lithium ion secondary battery of the present embodiment should not be limited to these.
  • FIG. 1 schematically shows the overall structure of a flat (stacked) lithium ion secondary battery (hereinafter also simply referred to as “stacked battery”), which is a typical embodiment of the electrical device of the present invention.
  • stacked battery a flat (stacked) lithium ion secondary battery
  • the stacked battery 10 of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate sheet 29 that is an exterior body.
  • the positive electrode in which the positive electrode active material layer 15 is disposed on both surfaces of the positive electrode current collector 12, the electrolyte layer 17, and the negative electrode active material layer 13 is disposed on both surfaces of the negative electrode current collector 11. It has a configuration in which a negative electrode is laminated. Specifically, the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 15 and the negative electrode active material layer 13 adjacent thereto face each other with the electrolyte layer 17 therebetween. .
  • the adjacent positive electrode, electrolyte layer, and negative electrode constitute one unit cell layer 19. Therefore, it can be said that the stacked battery 10 shown in FIG. 1 has a configuration in which a plurality of single battery layers 19 are stacked and electrically connected in parallel.
  • the positive electrode current collector 15 located on both outermost layers of the power generation element 21 has the positive electrode active material layer 15 disposed only on one side, but the active material layers may be provided on both sides. . That is, instead of using a current collector dedicated to the outermost layer provided with an active material layer only on one side, a current collector having an active material layer on both sides may be used as it is as an outermost current collector. Further, by reversing the arrangement of the positive electrode and the negative electrode as compared with FIG. 1, the outermost negative electrode current collector is positioned on both outermost layers of the power generation element 21, and one side of the outermost negative electrode current collector or A negative electrode active material layer may be disposed on both sides.
  • the positive electrode current collector 12 and the negative electrode current collector 11 are attached to the positive electrode current collector plate 27 and the negative electrode current collector plate 25 that are electrically connected to the respective electrodes (positive electrode and negative electrode), and are sandwiched between the end portions of the laminate sheet 29. Thus, it has a structure led out of the laminate sheet 29.
  • the positive electrode current collector 27 and the negative electrode current collector 25 are ultrasonically welded to the positive electrode current collector 12 and the negative electrode current collector 11 of each electrode via a positive electrode lead and a negative electrode lead (not shown), respectively, as necessary. Or resistance welding or the like.
  • the lithium ion secondary battery described above is characterized by a negative electrode.
  • main components of the battery including the negative electrode will be described.
  • the positive electrode active material layer 15 includes a positive electrode active material.
  • the positive electrode active material examples include LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , Li (Ni—Mn—Co) O 2, and lithium-- such as those in which some of these transition metals are substituted with other elements.
  • Examples include transition metal composite oxides, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds.
  • two or more positive electrode active materials may be used in combination.
  • a lithium-transition metal composite oxide is used as the positive electrode active material.
  • a composite oxide containing lithium and nickel is used, and more preferably Li (Ni—Mn—Co) O 2 and a part of these transition metals substituted with other elements (hereinafter, referred to as “following”) Simply referred to as “NMC composite oxide”).
  • the NMC composite oxide has a layered crystal structure in which a lithium atomic layer and a transition metal (Mn, Ni, and Co are arranged in order) are stacked alternately via an oxygen atomic layer.
  • One Li atom is contained, and the amount of Li that can be taken out is twice that of the spinel lithium manganese oxide, that is, the supply capacity is doubled, so that a high capacity can be obtained.
  • a represents the atomic ratio of Li
  • b represents the atomic ratio of Ni
  • c represents the atomic ratio of Mn
  • d represents the atomic ratio of Co
  • x represents the atomic ratio of M. Represents. From the viewpoint of cycle characteristics, it is preferable that 0.4 ⁇ b ⁇ 0.6 in the general formula (1).
  • the composition of each element can be measured by, for example, inductively coupled plasma (ICP) emission spectrometry.
  • ICP inductively coupled plasma
  • Ni nickel
  • Co cobalt
  • Mn manganese
  • Ti or the like partially replaces the transition metal in the crystal lattice. From the viewpoint of cycle characteristics, it is preferable that a part of the transition element is substituted with another metal element, and it is particularly preferable that 0 ⁇ x ⁇ 0.3 in the general formula (1). Since at least one selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr is dissolved, the crystal structure is stabilized. It is considered that the battery capacity can be prevented from decreasing even if the above is repeated, and that excellent cycle characteristics can be realized.
  • LiNi 0.8 Co 0.1 Al 0.1 O 2 is more advantageous in terms of a larger capacity, but there are difficulties in life characteristics.
  • LiNi 0.5 Mn 0.3 Co 0.2 O 2 has life characteristics as excellent as LiNi 1/3 Mn 1/3 Co 1/3 O 2 .
  • two or more positive electrode active materials may be used in combination.
  • a lithium-transition metal composite oxide is used as the positive electrode active material.
  • positive electrode active materials other than those described above may be used.
  • the positive electrode active material layer 15 may contain a binder.
  • polyvinylidene fluoride, polyimide, styrene / butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene, polyacrylonitrile, polyamide, and polyamideimide are more preferable.
  • These suitable binders are excellent in heat resistance, have a very wide potential window, are stable at both the positive electrode potential and the negative electrode potential, and can be used for the active material layer. These binders may be used alone or in combination of two.
  • the amount of the binder contained in the positive electrode active material layer is not particularly limited as long as it can bind the active material, but it is preferably 0.5 to 15% by mass with respect to the active material layer. More preferably, it is 1 to 10% by mass.
  • the positive electrode (positive electrode active material layer) can be applied by any one of a kneading method, a sputtering method, a vapor deposition method, a CVD method, a PVD method, an ion plating method, and a thermal spraying method in addition to a method of applying (coating) a normal slurry. Can be formed.
  • the negative electrode active material layer 13 includes a negative electrode active material.
  • the negative electrode active material has a ternary alloy composition represented by Si—Sn—M (M is one or more transition metal elements), and the microstructure is a transition metal.
  • a first phase mainly composed of silicide (silicide) and a second phase (partially tin (Sn)) mainly composed of amorphous or low crystalline Si ( Amorphous Si phase (a-Si phase)), part of which is a plurality of independent first phases and part of which is a eutectic structure of the first phase and the second phase. It consists of a silicon-containing alloy.
  • A is an inevitable impurity
  • M is one or more transition metal elements
  • the silicon-containing alloy (having a composition of Si x Sn y M z A a ) according to this embodiment is a ternary system of Si, Sn, and M (transition metal). is there.
  • the “inevitable impurities” means an Si-containing alloy that exists in a raw material or is inevitably mixed in a manufacturing process. The inevitable impurities are originally unnecessary impurities, but are a very small amount and do not affect the characteristics of the Si alloy.
  • M is preferably titanium (Ti).
  • Ti is one of silicide forming elements
  • M is preferably titanium (Ti).
  • the Si-based negative electrode active material when Si and Li are alloyed during charging, the Si phase changes from an amorphous state to a crystalline state, causing a large volume change (about 4 times). As a result, there is a problem that the active material particles themselves are broken and the function as the active material is lost. For this reason, by suppressing the phase transition of the Si-phase amorphous-crystal during charging, the collapse of the particles themselves can be suppressed, the function (high capacity) as an active material is maintained, and the cycle life is also improved. Can do.
  • the silicon-containing alloy according to this embodiment (having the composition of Si x Sn y M z A a ) is a ternary system of Si, Sn, and M (transition metal).
  • the sum of the constituent ratios (mass ratios x, y, z) of the constituent elements is 100% by mass, but there is no particular limitation on the values of x, y, z.
  • x is preferably 60 ⁇ x ⁇ 73, more preferably 60 ⁇ x ⁇ 70, from the viewpoint of maintaining durability against charging / discharging (insertion / desorption of Li ions) and a balance of initial capacity. More preferably, 60 ⁇ x ⁇ 65.
  • y is dissolved in the Si phase, and by increasing the distance between Si tetrahedrons in the Si phase, from the viewpoint of enabling reversible insertion and desorption of Li ions during charge and discharge, Preferably 2 ⁇ y ⁇ 15, more preferably 2 ⁇ y ⁇ 10, and further preferably 5 ⁇ y ⁇ 10.
  • Z is preferably 25 ⁇ z ⁇ 35, more preferably 27 ⁇ z, from the viewpoint of maintaining durability against charge / discharge (insertion / desorption of Li ions) and balancing the initial capacity, similarly to x. ⁇ 33, more preferably 28 ⁇ z ⁇ 30.
  • the M is composed of one or more transition metal elements containing Ti by containing a relatively large amount of Ti and containing Sn to some extent while containing Si as a main component.
  • the content of Ti in this phase can be greater than the content of transition metals (including Sn) excluding Ti in the second phase.
  • Si element-containing alloy negative electrode active material
  • Sn is sufficiently dispersed in a part of the Si phase. Since Si can be dissolved, the degree of Si being amorphous is large, and sufficient cycle durability can be obtained. Further, Sn that is not dispersed or dissolved in a part of the Si phase does not segregate as crystalline Sn in the Si phase, and does not segregate at the boundary between the silicide phase and the Si phase of the eutectic structure, and further independent.
  • A is an impurity (unavoidable impurity) other than the above three components derived from the raw materials and the manufacturing method.
  • the a is 0 ⁇ a ⁇ 0.5, and preferably 0 ⁇ a ⁇ 0.1.
  • the silicon-containing alloy constituting the negative electrode active material in the present embodiment has a fine structure of (1) a silicide phase (first phase) whose main component is a transition metal silicide (silicide). (2) a containing Sn in part (specifically, Sn dispersed (solid solution) inside the crystal structure of Si) and having amorphous or low crystalline Si as a main component -Si phase (second phase), (3) part of a plurality of independent first phases, and (4) part of the first and second phases are eutectic It is also unique in that it is an organization.
  • the silicon-containing alloy of the present embodiment has a configuration in which the second phase is eutectic with the first phase and further enters a plurality of independent first phase gaps.
  • the silicide phase (first phase) is superior in terms of hardness and electron conductivity compared to the a-Si phase (second phase). Therefore, it can be said that the effects of the present invention can be achieved by the following mechanism of action (see the drawing of the microstructure of Example 2).
  • the eutectic first phase suppresses the expansion of the a-Si phase (particularly the Si active material) in the eutectic structure in the charge / discharge process, and more
  • the independent first phase can be suppressed by a two-stage suppression.
  • the expansion and contraction of the silicon-containing alloy in the charge / discharge process is reduced, and the a-Si phase (second phase) and the eutectic are formed by the silicide phase (first phase) composed of conductive silicide.
  • the a-Si phase (particularly the Si active material) can be reacted uniformly.
  • cycle durability can be improved while showing the high capacity
  • the silicon-containing alloy constituting the negative electrode active material in the present embodiment has a silicide phase (silicide) containing a transition metal silicide (silicide) as a main component in the microstructure.
  • the first phase This silicide phase (first phase) is superior in terms of hardness and electronic conductivity compared to the a-Si phase (second phase). For this reason, the silicide phase (first phase) plays a role of maintaining the shape of the Si active material in the a-Si phase (second phase) against the stress during expansion, and the a-Si phase.
  • the low electronic conductivity of (especially the Si active material) can be improved (see the above action mechanism).
  • the silicide phase (first phase) includes a transition metal silicide (eg, TiSi 2 ), and thus has excellent affinity with the a-Si phase (second phase), and particularly has a volume during charging. Cracking at the (crystal) interface during expansion can be suppressed.
  • M is preferably titanium (Ti).
  • Ti titanium
  • the amorphous-crystal phase transition is further suppressed during Li alloying.
  • the cycle life can be improved.
  • the silicide phase (first phase) mainly composed of a transition metal silicide (silicide) in the microstructure is titanium silicide (TiSi 2 ).
  • silicide phase “having silicide as a main component” means 50 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more, particularly preferably 95 mass% of the silicide phase. % Or more, and most preferably 98% by mass or more is silicide. Ideally, the silicide is 100% by mass, but as shown in the elemental analysis table shown below the graph of FIG. 8B, in addition to Si and Ti, inevitably a very small amount of P, Since Sn and O are mixed, it is practically difficult to obtain a 100% by mass.
  • the silicon-containing alloy contains Sn in a part of the microstructure (specifically, Sn is dispersed and solidified in the crystal structure of Si). And an a-Si phase (second phase) mainly composed of amorphous or low crystalline Si (referred to as a-Si).
  • This a-Si phase (second phase) is a phase containing amorphous or low crystalline Si as a main component.
  • This a-Si phase (second phase; phase containing a-Si as a main component) is a phase involved in occlusion / release of lithium ions during operation of the electric device (lithium ion secondary battery) of this embodiment.
  • the a-Si phase (second phase) contains Si as a main component, a large amount of Li can be occluded and released per weight and per volume.
  • Sn in the a-Si phase (second phase) (Sn which is dispersed and dissolved in the Si crystal structure) is also more per weight and volume than the carbon negative electrode material (carbon negative electrode material).
  • carbon negative electrode material carbon negative electrode material
  • a large amount of Li can be occluded and released.
  • the a-Si phase (second phase) may contain a small amount of additive elements such as phosphorus and boron, transition metals, and the like.
  • the Si phase (second phase) mainly composed of amorphous or low crystallinity in the microstructure is preferably composed of amorphous Si as a main component.
  • the silicide of the first phase transition metal in the microstructure is titanium silicide (TiSi 2 ), and the Si phase (second phase) is amorphous. Si is the main component. With such a configuration, cycle durability can be further improved while showing a high capacity of the electric device.
  • “partially contains Sn” means that most of the Si phase contains Sn when compared with FIG. 7B to FIG. 7C. This is because there is no portion (the Si portion functions as an active material), but a portion containing Sn in the Si phase is seen in part. In the portion containing Sn in the Si phase, Sn is dispersed and dissolved in the Si crystal structure (the Sn—Si solid solution functions as an active material). Further, the remaining part of Sn in the eutectic structure is not an Si phase, but is crystallized in a silicide phase or a boundary part of the Si phase in the eutectic structure, and Sn phase (functioning as an active material) containing Sn as a main component. Form).
  • Sn phase active material Function as).
  • Sn as a main component means that 50% by mass or more of the Sn phase, preferably 80% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 98% by mass or more. Sn. Ideally, Sn is 100% by mass, but since a small amount of Si, Ti, and O is mixed in addition to Sn, it is practically difficult to obtain 100% by mass.
  • the silicon-containing alloy is partly a plurality of independent first phases in the microstructure. This is one of the features. Since a part of the microstructure is a plurality of independent silicide phases (first phases), the second phase (a -Si phase) expansion can be suppressed by a plurality of independent first phases. In addition, the low electronic conductivity of the a-Si phase (particularly the Si active material) can be improved.
  • the silicon-containing alloy is obtained by melting a predetermined alloy raw material by a liquid quenching roll solidification method, quenching at a predetermined cooling rate, and alloying, so that a plurality of independent first phases become primary crystals in the liquid phase. Crystallization is obtained by crystallizing the eutectic structure of the first phase and the second phase in the liquid phase in the gap between the independent first phases.
  • a plurality of phases may exist in each of the above-described plurality of independent silicide phases (first phases) and silicide phases (first phases) in the eutectic structure, for example, transition metal elements
  • Two or more phases for example, MSi 2 and MSi
  • two or more phases may exist by including a silicide with different transition metal elements.
  • the type of transition metal contained in the silicide phase (first phase) is not particularly limited, but is preferably at least one selected from the group consisting of Ti, Zr, Ni, Cu, and Fe, and more Ti or Zr is preferable, and Ti is particularly preferable.
  • These elements exhibit higher electronic conductivity and higher strength than silicides of other elements when silicides are formed.
  • TiSi 2 which is silicide when the transition metal element is Ti is preferable because it exhibits very excellent electron conductivity.
  • microstructure of the silicon-containing alloy has the above-described configuration (structure) is, for example, observation with a high-resolution STEM (scanning transmission electron microscope), elemental analysis by EDX (energy dispersive X-ray spectroscopy), electron diffraction Measurement and EELS (Electron Energy Loss Spectroscopy) measurement can reveal the microstructure of the silicon-containing alloy (particles) that are the negative electrode active material particles.
  • analyzers include XPS (X-ray photoelectron spectroscopy), TEM-EDX (transmission electron microscope-energy dispersive X-ray spectroscopy), and STEM-EDX / EELS (scanning transmission electron microscope).
  • Energy dispersive X-ray spectroscopy / electron energy loss spectrometer can be used.
  • HAADF-STEM high angle scattering dark field-scanning transmission electron microscope image
  • the silicon-containing alloy (particles) that are the negative electrode active material particles prepared in Example 2 will be described as an example, but the silicon-containing alloy that is the negative electrode active material particles obtained in this embodiment will be described.
  • the structure of the microstructure of the alloy (particle) can be clarified for the alloy (particle).
  • Analysis method 1-1 Sample preparation FIB (focused ion beam) method; Microsampling system (manufactured by Hitachi, Ltd., FB-2000A) An Al grid is used.
  • STEMimage, EDX, EELS (Electron Energy Loss Spectroscopy) measuring apparatus and conditions are as follows.
  • Equipment Atomic resolution analytical electron microscope JEOL JEM-ARM200F EDX (Energy dispersive X-ray Spectroscopy) ; JED-2300 made by JEOL (100mm 2 silicon drift (SDD) type) ; System; Analysis Station EELS (Electron Energy Loss Spectroscopy) GATAN GIF Quantum Image acquisition: Digital Micrograph 2) Measurement conditions; acceleration voltage: 200 kV Beam diameter: about 0.2nm ⁇ (diameter) Energy resolution: about 0.5eV FWHM 1-3: Electron diffraction measurement apparatus and conditions are as follows.
  • FIG. 3A shows the silicon-containing alloy of the present embodiment.
  • 1 is a drawing showing a BF (Bright-field) -STEM Image (bright field-scanning transmission electron microscope image) (low magnification) of a sample prepared by FIB method (particles).
  • FIG. 1 is a drawing showing a BF (Bright-field) -STEM Image (bright field-scanning transmission electron microscope image) (low magnification) of a sample prepared by FIB method (particles).
  • FIG. 3B shows a HAADF-STEM Image (high angle scattering dark field-scanning transmission electron microscope image) of the active material particles in the same field of view as FIG.
  • D50 7 ⁇ m
  • D90 20 ⁇ m
  • FIG. 4 is a drawing showing quantitative mapping data by STEM-EDX (scanning transmission electron microscope-energy dispersive X-ray spectroscopy).
  • FIG. 4 (a) is the same HAADF-STEM image as FIG. 3 (b).
  • FIG. 4B is a diagram showing mapping data of Sn (lower left) measured in the same field of view as HAADF-STEM (upper left FIG. 4A).
  • FIG. 4C is a diagram showing mapping data of Si (lower center) measured in the same field of view as HAADF-STEM (upper left FIG. 4A).
  • FIG. 4D is a drawing showing mapping data of Ti (lower right) measured in the same field of view as HAADF-STEM (upper left FIG. 4A).
  • FIG. 4 is a drawing showing quantitative mapping data by STEM-EDX (scanning transmission electron microscope-energy dispersive X-ray spectroscopy).
  • FIG. 4 (a) is the same HAADF-STEM image as FIG. 3 (b).
  • 4 (e) is a diagram (upper right) in which mapping data of Sn, Si, and Ti measured in the same field of view as HAADF-STEM (upper left FIG. 4 (a)).
  • 4B-4E can actually be colored (colored). For example, if Sn is green, Si is blue, and Ti is red, silicide (TiSi 2 ) is Since the blue of Si and the red of Ti are mixed, it can be distinguished at a glance. However, in the application drawing, it is necessary to submit a black and white image. These are included in FIG. 3B and FIG. 4E.
  • a bright-field (BF) STEM image formed using an electron beam transmitted through a sample and a dark field formed using an electron beam scattered from the sample
  • DF dark-field
  • FIG. 3A the transmission composition showing the internal structure of the sample, as in the case of a normal TEM image
  • HAADF high angle scattering annular dark field
  • Z atomic number
  • Substances with large atomic numbers appear bright (FIG. 3 (b), FIG. 4 (a), FIG. 5 (b), FIG. 6 (b), FIG. 7 (a), FIG. 8 (a), FIG. 9 (a) reference).
  • HAADF-STEM High Angle Scattering Circular Dark Field Scanning Transmission Microscopy
  • the image is applied by operating a thinly focused electron beam while operating the sample, and the scattered electrons are detected at a high angle by a ring detector. can get. Since a material having a large Z 2 ⁇ is scattered at a higher angle, heavier elements are darker in the STEM image and brighter in the HAADF-STEM image. Since a contrast proportional to the atomic weight (Z) is obtained, it is also called a Z contrast image.
  • STEM-EDX quantitative mapping characteristic X-rays generated from each point are taken into an EDS (Energy-Dispersive-Spectroscope) detector while narrowing down the electron beam and scanning the sample, thereby obtaining information on the composition distribution of the sample. Can be obtained.
  • EDS Electronic-Dispersive-Spectroscope
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • the silicide phase (first phase) and the surrounding area on the right side in the microstructure of the sample and the vicinity thereof are
  • the Si phase containing the Sn (second phase) is a eutectic structure (a (solid solution) crystal, amorphous or low crystallinity with different component ratios), and the first phase and the second phase are mixed. It can be confirmed that the organization is matched.
  • the (relatively small) gray portion corresponding to (phase) is mixed.
  • the fine Si phase and the silicide phase are co-crystallized (having a eutectic structure).
  • the eutectic structure can be confirmed by the following when colored.
  • the enclosed portion on the right side and the (relatively small) dark gray portion (second phase) in the vicinity of the surrounding area mainly contain Si blue (including a small amount of Sn) or Si blue and Sn green.
  • the silicide phase (first phase) mainly composed of the transition metal silicide (silicide) of the above (1), Part (2) above includes Sn, and more specifically, the main component is amorphous or low crystalline Si (which is formed by dispersing and solid-dissolving Sn inside the Si crystal structure). It can be confirmed that a part of the above (4) has a eutectic structure of the first phase and the second phase.
  • FIG. 4 (b) the white part in FIG. 4 (a) is Sn in which Sn that has not been dispersed and dissolved in the second phase of amorphous or low crystalline Si has crystallized. It is a phase (may contain trace amounts of Si and Ti). Such an Sn phase may crystallize in a portion other than the independent first phase and the eutectic structure (portion other than the left and right enclosed portions in FIG. 3B), or the eutectic structure (FIG. 3B ) May be crystallized in a portion other than the first phase and the second phase.
  • 5B is the silicide (TiSi 2 ) phase (first phase) in the eutectic structure, and the dark gray (or black) portion contains Sn in a part of the eutectic structure. It is an a-Si phase (second phase), and the whitish portion is an Sn phase mainly composed of Sn (dispersed in the second phase and crystallized without being completely dissolved). For some of these, an arrow in FIG. 5B indicates whether it corresponds to TiSi 2 (silicide phase), Si (a-Si phase containing Sn), or Sn (Sn phase). Yes.
  • FIG. 6A shows a BF (Bright-field) -STEM Image (bright-field-scanning transmission electron microscope image) obtained by further enlarging a part of the eutectic structure of the silicon-containing alloy (particle) of this embodiment. It is a drawing (high magnification).
  • FIG. 6B is a drawing showing a HAADF-STEM Image (high angle scattering dark field-scanning transmission electron microscope image) of the active material particles in the same field of view as FIG.
  • FIG. 7B to 7E can actually be colored (colored), for example, if Sn is green, Si is blue, and Ti is red, silicide (TiSi 2 ) is Since the blue of Si and the red of Ti are mixed, it can be distinguished at a glance. However, in the application drawing, it is necessary to submit a black and white image. These are included in FIG. 6B and FIG. 7E. Those skilled in the art can easily obtain the same analysis information from quantitative mapping data by STEM-EDX (scanning transmission electron microscope-energy dispersive X-ray spectroscopy) as in FIG. It is because it can be obtained.
  • STEM-EDX scanning transmission electron microscope-energy dispersive X-ray spectroscopy
  • FIGS. 7A and 7E black is shown in FIG. 7A corresponding to the Si phase (second phase) partially containing Sn, and a dark gray portion (Si + Sn in FIG. 7E). It can be confirmed that the portion) and the gray portion corresponding to the silicide phase (first phase) are mixed. From this, it can be seen that the fine Si phase and the silicide phase are co-crystallized (having a eutectic structure). The eutectic structure can be confirmed by the following when colored. That is, the dark gray portions (second phase) in the upper left, upper right, lower center, etc. of FIG. 7E are mainly Si blue (including a small amount of Sn) or Si blue and Sn green.
  • the gray portion (first phase) in the center, lower left, upper right, lower left, etc. in FIG. 7E is pink in which Si blue and Ti red are mixed.
  • a blue or blue-green portion corresponding to the Si phase (second phase) containing Sn in part and a pink portion corresponding to the silicide phase (first phase) are mixed. It can be confirmed that these are eutectic structures.
  • FIGS. 8 and 9 are the same HAADF-STEM images as FIG. 6 (b) and FIG. 7 (a). Yes, the region (two places surrounded by a square frame) where the presence of the element in the silicide phase (first phase) and the element in the Si phase (second phase) observed by elemental analysis is shown in the image The figure is divided into numbers 1 and 2.
  • FIG. 8 (a) is the same HAADF-STEM image as FIG. 6 (b) and FIG. 7 (a), and the rectangular frame of the portion to be observed for the element distribution (the portion of the circled number 1 in the image). Is a drawing indicated by a bold line.
  • FIG. 8B is a drawing in which elemental analysis is performed on a portion to be observed of the element distribution of FIG.
  • FIG. 8C is an elemental analysis table summarizing the elemental analysis results of FIG.
  • the Si element peak and the Ti element peak are observed in the circled number 1 portion (silicide phase portion) of FIG.
  • the Sn element peak is hardly observed.
  • FIGS. 8B and 8C it was confirmed that Si and Ti exist at an atomic ratio of approximately 2: 1. Also from this, it can be confirmed that the gray portion including the circled portion 1 is silicide (TiSi 2 phase). Note that, from FIG. 8B, the circled number 1 portion (silicide phase portion) of FIG. 8A inevitably contains a trace amount of Sn element and P element.
  • FIG. 9 (a) is the same HAADF-STEM image as FIG. 6 (b) and FIG. 7 (a), and the rectangular frame of the portion to be observed for the element distribution (the portion indicated by the round numeral 2 in the image). Is a drawing indicated by a bold line.
  • FIG. 9B is a drawing in which elemental analysis is performed on a portion to be observed of the element distribution of FIG. 9A.
  • FIG. 9C is an element analysis table summarizing the elemental analysis results of FIG.
  • FIG. 10 (b) is an enlarged view of a part of the eutectic structure in the right enclosing portion of FIG. 10 (a), and the same HAADF-STEM Image (high angle scattering dark field as in FIG. 6 (b)). -Scanning transmission electron microscope image).
  • FIG. 10C is a diffraction pattern obtained by performing fast Fourier transform processing on an independent silicide phase region in the left enclosing portion of FIG. 10A by electron diffraction measurement.
  • FIG. 10D is a diffraction pattern obtained by subjecting the region of the a-Si phase in the eutectic structure of FIG. 10B to fast Fourier transform by electron diffraction measurement.
  • FIG. 10C is a diffraction pattern obtained by performing fast Fourier transform processing on an independent silicide phase region in the left enclosing portion of FIG. 10A by electron diffraction measurement.
  • FIG. 10D is a diffraction pattern obtained by subjecting the region of
  • FIG. 10E is a diffraction pattern obtained by performing a fast Fourier transform process on the silicide phase region in the eutectic structure of FIG. 10B by electron diffraction measurement.
  • FIG. 11 is a chart obtained by (powder) X-ray diffraction (XRD) measurement of the same alloy of Example 2 as FIG. 10 (a) and 10 (b) are the same as those described with reference to FIGS. 3 (b) and 6 (b), and a description thereof is omitted here.
  • Observation target 10 and 11 as described above, an alloy represented by the alloy composition Si 60 Sn 10 Ti 30 of the second embodiment.
  • a net pattern (lattice spot) of a two-dimensional point array is obtained for a single crystal phase, and a Debye-Scherrer ring (diffraction ring) for a polycrystalline phase.
  • a halo pattern is obtained for the amorphous phase.
  • the crystal structure of the two-dimensional dot array net pattern (silicide phase) can be specified. That is, from the diffraction patterns shown in FIG. 10C and FIG. 10E, a net pattern of a two-dimensional point array is obtained, and it can be confirmed that it is a single crystal phase. Furthermore, from the diffraction patterns shown in FIGS.
  • the crystal structure of the silicide phase (silicide) in the independent silicide phase and eutectic structure, which is a single crystal phase, is a C49 structure.
  • XRD X-ray diffraction
  • the strength is mutually complemented by suppressing it in the above-described two-stage manner. It can be said that the excellent cycle durability can be effectively expressed by the mutual action. That is, while the main component C49 structure low hardness silicide allows the expansion of Si to some extent, the secondary component C54 structure high-strength silicide blocks further expansion of Si, thereby increasing the capacity and durability. It can be said that it is a composite structure that complements each other. As a result, it can be said that excellent cycle durability can be effectively expressed while maintaining a high capacity. Further, from the diffraction pattern shown in FIG.
  • the Si phase (second phase) in the eutectic structure has a Debye-Scherrer ring (diffraction ring) and is a polycrystalline phase. . Furthermore, since a diffractive ring having a halo pattern is obtained, it can be confirmed that the Si phase (second phase) is an amorphous phase having amorphous or low crystalline Si (a-Si). That is, the Si phase (second phase) in the eutectic structure has amorphous or low crystalline Si (a-Si) by making it amorphous, as shown in FIG. This can be confirmed by electron diffraction analysis.
  • a-Si phase (second phase) is more amorphous than the silicide phase (first phase) is confirmed by the diffraction patterns of FIGS. 10 (d), 10 (c) and 10 (e). can do.
  • an independent silicide phase which is a single crystal phase and a crystal structure of the silicide phase (silicide) in the eutectic structure is a C49 structure
  • an Si phase (second phase) in the eutectic structure is non-crystalline.
  • the Si phase (second phase) in the eutectic structure has amorphous or low crystalline Si (a-Si) by making it amorphous.
  • the size of the independent first phase in the microstructure of the alloy is It is preferable that it is larger than the size of the eutectic structure of the first phase and the second phase. This is because by having such a configuration, the effects of the present invention can be more effectively expressed by the above-described action mechanism. That is, a relatively small-sized eutectic structure (the second phase is eutectic with the first phase) enters a gap between a plurality of independent relatively large-sized first phases in the microstructure. It can be configured.
  • the size of the independent first phase is lower than that in the transmission electron micrograph (for example, FIG. 3B), and the independent first phase is observed more than the number standard by observation at a plurality of locations.
  • the size of the eutectic structure means the total size (one unit size) of one first phase and one second phase adjacent to each other in the eutectic structure.
  • the size of the eutectic structure is also the average equivalent circular diameter of 100 first phases on a number basis measured by the equivalent circular diameter from a transmission electron micrograph.
  • a transmission electron micrograph for example, a lower magnification than that in FIG. 3B or FIG. It may be used.
  • the magnification is higher than that in FIG. 3B (see, for example, FIG. 5B and FIG. 6B), and the independent first phase is observed more than the number standard by observation at a plurality of locations. Also good.
  • the size of the first independent phase is clearly larger than the size of the eutectic structure (one unit) of the first phase and the second phase.
  • the size of the first phase and the second phase in the eutectic structure is also referred to as the total size (size of one unit).
  • the size (average particle diameter) of the first phase and the second phase in the eutectic structure is also an average particle of 100 particles on the number basis measured by an equivalent circular diameter from a transmission electron micrograph. Is the diameter.
  • the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure in the silicon-containing alloy (particles) of the present embodiment, in the microstructure of the alloy.
  • the size of the first phase (silicide phase) is the mode radius of 500 nm or less
  • the size of the Si phase (second phase) in the eutectic structure of the first phase and the second phase is the mode. It is preferable that the radius is less than 110 nm.
  • the effects of the present invention can be more effectively expressed by the above-described action mechanism. That is, a structure in which a eutectic structure in which a relatively small second phase and a first phase are co-crystallized enters a gap between a plurality of independent relatively large first phases in a microstructure. can do. Further, the first phase (silicide phase) is superior in terms of hardness and electronic conductivity as compared with the second phase (Si phase). Therefore, expansion of a relatively small Si phase (active material) in the eutectic structure during the charge / discharge process can be more effectively suppressed. This is because the eutectic relatively small first phase (see FIGS.
  • the size of the independent first phase (silicide phase) in the microstructure of the alloy is preferably a mode radius of preferably 450 nm or less, more preferably 400 nm or less, still more preferably 350 nm or less, and particularly preferably 240 nm or less.
  • the lower limit of the mode radius of the size of the independent first phase (silicide phase) is not particularly limited, but is preferably 160 nm or more, more preferably 170 nm or more, still more preferably 180 nm or more, and particularly preferably 190 nm or more. It is.
  • the size of the Si phase (second phase) in the eutectic structure is preferably a mode radius of preferably 100 nm or less, more preferably 85 nm or less, still more preferably 70 nm or less, particularly preferably less than 50 nm, and particularly preferably. Is 48 nm or less.
  • the lower limit of the mode radius of the size of the Si phase (second phase) in the eutectic structure is not particularly limited, but is preferably 25 nm or more, more preferably 30 nm or more, still more preferably 35 nm or more, particularly Preferably it is 40 nm or more.
  • the size of the independent first phase (silicide phase) is preferably a radial distribution of 80 to 1000 nm, more preferably 85. It is in the range of ⁇ 900 nm, more preferably 90 to 800 nm, particularly preferably 95 to 700 nm, and particularly preferably 100 to 480 nm.
  • the size of the Si phase (second phase) in the eutectic structure is preferably 5 to 200 nm, more preferably 8 to 190 nm, still more preferably 10 to 180 nm, and particularly preferably less than 12 to 170 nm in the radius distribution. In particular, the range of 15 to 160 nm is preferable.
  • the mode radius and the radius distribution of the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure are determined by the following procedure. Can be calculated.
  • Si—Sn—M ternary alloys of the compositions of Examples 1 to 4 and Comparative Example 1 will be described as Si—Sn—M alloys, but other alloys are also subjected to the following procedure. Thus, it can be calculated in the same manner.
  • thermodynamic calculation system Thermo-Calc Ver2015a made by Thermo-Calc software AB of Sweden (Japanese agency: ITOCHU Techno-Solutions Corporation) is used as a thermodynamic database.
  • the precipitation phase is primary TiSi 2 silicide and eutectic (TiSi 2 + Si (diamond_A4)), and in the composition of Comparative Example 1, the calculation result is eutectic (TiSi 2 + Si). Obtained.
  • FIG. 12 shows a Si—Sn—Ti ternary equilibrium diagram when the Si—Sn—Ti ternary alloy temperature is 1400 ° C.
  • FIG. 13 shows a Si—Sn—Ti ternary equilibrium diagram when the temperature of the Si—Sn—Ti ternary alloy is 1450 ° C.
  • FIG. 14 shows a Si—Sn—Ti ternary equilibrium diagram when the temperature of the Si—Sn—Ti ternary alloy is 1300 ° C.
  • FIG. 15 shows an Si—Sn—Ti ternary equilibrium diagram when the temperature of the Si—Sn—Ti ternary alloy is 1200 ° C.
  • FIG. 12 shows a Si—Sn—Ti ternary equilibrium diagram when the Si—Sn—Ti ternary alloy temperature is 1400 ° C.
  • FIG. 13 shows a Si—Sn—Ti ternary equilibrium diagram when the temperature of the Si—Sn—Ti ternary alloy is 1450 ° C.
  • FIG. 16 is a diagram in which analysis information is included in the state diagram of FIG.
  • FIG. 17 is a drawing in which analysis information is included in a Si—Sn—Ti ternary equilibrium diagram at a Si—Sn—Ti ternary alloy temperature of 1310 ° C.
  • FIG. 18 is a liquid phase projection view of the Si—Sn—Ti ternary system by Thermo-Calc (integrated thermodynamic calculation system).
  • the location of the alloy composition of Si 60 Sn 10 Ti 30 of Examples 2 to 4 is indicated by an arrow. Since the location is on the region where the crystallization of TiSi 2 is observed as the primary crystal in the liquid phase or on the solid phase line, “Si60Sn10Ti30: liq + Primary: TiSi2”. Moreover, the location of the alloy composition of Si 60 Sn 20 Ti 20 of Comparative Example 1 is indicated by an arrow, and since the location is in the liquid phase region, “Si60Sn20Ti20 (liquid)” is set.
  • the location of the alloy composition of Si 60 Sn 20 Ti 20 of Comparative Example 1 is indicated by an arrow, and since the location is on a region where the eutectic crystallization of Si and TiSi 2 is observed or on a solid line, “Si60Sn20Ti20 "Electric Si-TiSi2".
  • the location of the alloy composition of Si 60 Sn 30 Ti 10 having a Sn composition ratio larger than that of Comparative Example 1 is indicated by an arrow, and this location is crystallized (crystalline) Si as a primary crystal in the liquid phase. “Si60Sn10Ti30 liq + Cry-Si)” because it is in the recognized region or solid phase line.
  • FIG. 18 is a liquid phase projection showing the time until the molten alloy at 1500 ° C. is cooled to 1300 ° C. with an isothermal interval of 25 ° C.
  • Figures 18 instructs the location of the alloy composition of Si 60 Sn 10 Ti 30 of Examples 2-4 by the arrows, that location is observed crystallisation of eutectic primary crystal TiSi 2, and Si and TiSi 2 Therefore, “Si60Sn10Ti30 primary crystal TiSi2 + eutectic” is used.
  • the location of the alloy composition of Si 60 Sn 20 Ti 20 of Comparative Example 1 is indicated by an arrow, and since the location is in a region where eutectic crystallization of Si and TiSi 2 is observed, “Si60Sn20Ti20 eutectic Si”. -TiSi2 ".
  • the location of the alloy composition of Si 60 Sn 30 Ti 10 having a Sn composition ratio larger than that of Comparative Example 1 is indicated by an arrow, and this location is the primary crystal Si and the eutectic crystallization of Si and TiSi 2. Since it exists in the area
  • Example 1 In the precipitation calculation, the calculation was performed under the conditions of Examples 1 to 4 and Comparative Example 1. The calculation was performed under the following calculation conditions and temperature profile (Examples 1 to 4). The temperature profile of Comparative Example 1 is the same as that of Example 2.
  • Alloy composition (mass%): Si 65 Sn 5 Ti 30 (Example 1) Si 60 Sn 10 Ti 30 (Examples 2 to 4) Si 60 Sn 20 Ti 20 (Comparative Example 1)
  • Matrix / precipitation phase Liquid / TiSi 2 , Si (diamond_A4) (Crystallized in liquid phase)
  • Nuclear growth model Simply Nucleation site: Bulk (both TiSi 2 and Si (dia))
  • Interfacial energy Use estimated value from thermodynamic DB Phase boundary / mobility: Use dynamics DB data Mother phase / precipitate phase volume: 1E-4 (1 ⁇ 10 ⁇ 4 ) m 3 for both .
  • FIG. 19 is a diagram showing a state in which the temperature of the quenched ribbon alloy obtained by the apparatus used in the liquid quenched roll solidification method is observed using an infrared thermograph.
  • the mother alloy mother alloys of Examples 1 to 4
  • the mother alloy is sprayed from a quartz nozzle containing a mother alloy melted at 1450 ° C. onto a Cu roll having a rotational speed of 4000 rpm (peripheral speed: 41.9 m / second). This is an observation of the temperature of a ribbon-like alloy formed continuously horizontally from above the roll.
  • FIG. 20 is a graph plotting the temperature of the quenched ribbon alloy at positions (distances) every 2.25 mm from the nozzle for Examples 2 and 4.
  • FIG. 21 shows the number of rotations of the roll and the cooling time of the quenched ribbon alloy (from 1450 ° C. to 1100 ° C.) in FIG. ) A graph showing the relationship with temperature. In FIG. 20, only Examples 2 and 4 are plotted, but the temperature profile shown in FIG. 21 can be obtained by similarly plotting other Examples.
  • Example 1 it can be calculated as 1450 ° C. ⁇ 1100 ° C./5.67 ⁇ 10 ⁇ 5 seconds (cooling rate 6.2 ⁇ 10 6 ° C./second).
  • Example 2 it can be calculated as 1450 ° C. ⁇ 1100 ° C./7.56 ⁇ 10 ⁇ 5 seconds (cooling rate 4.6 ⁇ 10 6 ° C./second).
  • Example 3 can be calculated as 1450 ° C. ⁇ 1100 ° C./1.62 ⁇ 10 ⁇ 4 seconds (cooling rate 2.2 ⁇ 10 6 ° C./second).
  • Example 4 it can be calculated as 1450 ° C. ⁇ 1100 ° C./2.16 ⁇ 10 ⁇ 4 seconds (cooling rate 1.6 ⁇ 10 6 ° C./second).
  • FIG. 22 (a) shows the alloy composition of Si 65 Sn 5 Ti 30 of Example 1 and the size of the independent first phase obtained by the above precipitation calculation by applying the calculation conditions of Example 1 above. It is a graph which shows the mode radius of the size of Si phase (second phase) in a crystal structure.
  • FIG. 22B is a graph obtained by enlarging the graph of FIG. 22A and obtaining the radial distribution of the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure. is there. From the graph of FIG. 22A, the mode radius of the size of the Si phase (second phase) constituting the eutectic structure is 45 nm.
  • the silicide phase is a bimodal graph.
  • the peak with the smaller radius has a peak at almost the same position as the most frequent radius of the Si phase, and considering the observation results shown in FIGS. 3 to 9, the peak shows the eutectic structure. It is a silicide phase (first phase) to be formed, and the mode radius of the size is 60 nm.
  • the peak on the larger radius side is the size of the independent silicide phase (first phase), and the most frequent radius is 220 nm. From the graph of FIG. 22B, the radius distribution of the size of the Si phase (second phase) constituting the eutectic structure is 25 to 80 nm.
  • the radius distribution of the size of the silicide phase (first phase) constituting the eutectic structure is 40 to 90 nm, and the radius distribution of the size of the independent silicide phase (first phase) is 160 nm. ⁇ 300 nm.
  • the radius distribution reads a portion having a height of 5% with respect to the peak height.
  • FIG. 23 is a drawing showing a cross-sectional SEM (scanning electron microscope) image of the rapidly cooled ribbon alloy of Si 65 Sn 5 Ti 30 in Example 1.
  • the gray portion in FIG. 23 is the independent silicide phase (first phase) portion, and the black portion is the eutectic structure portion.
  • the white part is the Sn phase part.
  • the intermediate circle of the mode diameter based on the mode radius of the size of the Si phase (second phase) in the eutectic structure obtained from FIG. 22 and the maximum circle and the minimum circle based on the radius distribution are shown in FIG.
  • the method can be applied to the HAADF-STEM Image drawing of Example 1 which can be obtained in the same manner as in FIG.
  • the intermediate circle of the mode diameter based on the mode radius of the size of the Si phase (second phase) in these eutectic structures and the maximum circle and minimum circle based on the radius distribution are the actual Si phase (first phase). It can be confirmed that the equivalent circular diameter (average value and diameter distribution) of the second phase almost matches.
  • FIG. 24A shows the alloy composition of Si 60 Sn 10 Ti 30 of Example 2 and the size of the independent first phase obtained by the above precipitation calculation by applying the calculation conditions of Example 2 above. It is a graph which shows the mode radius of the size of Si phase (second phase) in a crystal structure.
  • FIG. 24B is a graph obtained by enlarging the graph of FIG. 24A and obtaining the radius distribution of the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure. is there. From the graph of FIG. 24A, the mode radius of the size of the Si phase (second phase) constituting the eutectic structure is 50 nm.
  • the silicide phase is a bimodal graph.
  • the peak with the smaller radius has a peak at almost the same position as the most frequent radius of the Si phase, and considering the observation results shown in FIGS. 3 to 9, the peak shows the eutectic structure. It is a silicide phase (first phase) to be formed, and the mode radius of the size is approximately 50 nm. Moreover, the peak on the larger radius side is the size of the independent silicide phase (first phase), and the most frequent radius is 250 nm. From the graph of FIG. 24B, the radius distribution of the size of the Si phase (second phase) constituting the eutectic structure is 30 to 90 nm.
  • the radius distribution of the size of the silicide phase (first phase) constituting the eutectic structure is also approximately 30 to 90 nm (not shown), and the independent silicide phase (first phase)
  • the size radius distribution is 190-340 nm.
  • the radius distribution is assumed to read a portion having a height of 5% with respect to the peak height.
  • FIG. 25 is a drawing showing a cross-sectional SEM (scanning electron microscope) image of the quenched ribbon alloy of Si 60 Sn 10 Ti 30 in Example 2.
  • the gray portion in FIG. 25 is the independent silicide phase (first phase) portion, and the black portion is the eutectic structure portion.
  • the white part is the Sn phase part.
  • the intermediate circle (diameter 500 nm) having the most frequent diameter substantially matched the actual equivalent circular diameter (average value) of the intermediate size of the first phase.
  • the maximum circle (diameter 680 nm) and the minimum circle (diameter) based on the radius distribution (190 to 340 nm) of the size of the independent first phase obtained by the precipitation calculation by applying the calculation conditions of Example 2 above.
  • these maximum circles (diameter 680 nm) and minimum circles (diameter 380 nm) almost coincide with the large size and the small equivalent circle diameter (diameter distribution) of the actual independent first phase.
  • the intermediate circle of the mode diameter based on the mode radius of the size of the Si phase (second phase) in the eutectic structure obtained from FIG. 24, the maximum circle and the minimum circle based on the radius distribution are shown in FIG. It can be applied to the HAADF-STEM Image drawing of Example 2 shown in FIG. As a result, the intermediate circle of the mode diameter based on the mode radius of the size of the Si phase (second phase) in these eutectic structures and the maximum circle and minimum circle based on the radius distribution are the actual Si phase (first phase). It can be confirmed that the equivalent circular diameter (average value and diameter distribution) of the second phase almost matches.
  • FIG. 26A shows the alloy composition of Si 60 Sn 10 Ti 30 of Example 3 and the size of the independent first phase obtained by the above precipitation calculation by applying the calculation conditions of Example 3 above. It is a graph which shows the mode radius of the size of Si phase (second phase) in a crystal structure.
  • FIG. 26B is a graph obtained by enlarging the graph of FIG. 26A and obtaining the radius distribution of the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure. is there. From the graph of FIG. 26A, the mode radius of the size of the Si phase (second phase) constituting the eutectic structure is 75 nm.
  • the silicide phase is a bimodal graph.
  • the peak with the smaller radius has a peak at almost the same position as the most frequent radius of the Si phase, and considering the observation results shown in FIGS. 3 to 9, the peak shows the eutectic structure. It is a silicide phase (first phase) to be formed, and the mode radius of the size is also approximately 75 nm.
  • the peak on the larger radius side is the size of the independent silicide phase (first phase), and the most frequent radius is 370 nm. From the graph of FIG. 26B, the radius distribution of the size of the Si phase (second phase) constituting the eutectic structure is 40 to 120 nm.
  • the radius distribution of the size of the silicide phase (first phase) constituting the eutectic structure is also approximately 40 to 120 nm (not shown), and the independent silicide phase (first phase)
  • the size radius distribution is 250-510 nm.
  • the radius distribution reads a portion having a height of 5% with respect to the peak height.
  • FIG. 27 is a drawing showing a cross-sectional SEM (scanning electron microscope) image of the quenched ribbon alloy of Si 60 Sn 10 Ti 30 in Example 3.
  • the gray portion in FIG. 27 is the independent silicide phase (first phase) portion, and the black portion is the eutectic structure portion.
  • the white part is the Sn phase part.
  • the intermediate circle of the mode diameter based on the mode radius of the size of the Si phase (second phase) in the eutectic structure obtained from FIG. 26, the maximum circle and the minimum circle based on the radius distribution are shown in FIG. This can be applied to the HAADF-STEM Image drawing of Example 3 which can be obtained in the same manner as in FIG.
  • the intermediate circle of the mode diameter based on the mode radius of the size of the Si phase (second phase) in these eutectic structures and the maximum circle and minimum circle based on the radius distribution are the actual Si phase (first phase). It can be confirmed that the equivalent circular diameter (average value and diameter distribution) of the second phase almost matches.
  • FIG. 28A shows the alloy composition of Si 60 Sn 10 Ti 30 of Example 4 and the size of the independent first phase obtained by the above precipitation calculation by applying the calculation conditions of Example 4 above. It is a graph which shows the mode radius of the size of Si phase (second phase) in a crystal structure.
  • FIG. 28B is a graph obtained by enlarging the graph of FIG. 28A and obtaining the radius distribution of the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure. is there. From the graph of FIG. 28A, the mode radius of the size of the Si phase (second phase) constituting the eutectic structure is 90 nm.
  • the silicide phase is a bimodal graph.
  • the peak with the smaller radius has a peak at almost the same position as the most frequent radius of the Si phase, and considering the observation results shown in FIGS. 3 to 9, the peak shows the eutectic structure. It is a silicide phase (first phase) to be formed, and the mode radius of the size is approximately 90 nm.
  • the peak on the larger radius side is the size of the independent silicide phase (first phase), and the mode radius is 420 nm (see FIG. 28B). From the graph of FIG. 28B, the radius distribution of the size of the Si phase (second phase) constituting the eutectic structure is 50 to 140 nm.
  • the radius distribution of the size of the silicide phase (first phase) constituting the eutectic structure is also approximately 50 to 140 nm (not shown), and the independent silicide phase (first phase)
  • the size radius distribution is 300 to 570 nm.
  • the radius distribution reads a portion having a height of 5% with respect to the peak height.
  • FIG. 29 is a drawing showing a cross-sectional SEM (scanning electron microscope) image of the quenched ribbon alloy of Si 60 Sn 10 Ti 30 of Example 4.
  • the gray portion in FIG. 29 is the independent silicide phase (first phase) portion, and the black portion is the eutectic structure portion.
  • the white part is the Sn phase part.
  • the intermediate circle of the mode diameter based on the mode radius of the size of the Si phase (second phase) in the eutectic structure obtained from FIG. 28, the maximum circle and the minimum circle based on the radius distribution are shown in FIG.
  • the method can be applied to the HAADF-STEM Image drawing of Example 4 which can be obtained in the same manner as in FIG.
  • the intermediate circle of the mode diameter based on the mode radius of the size of the Si phase (second phase) in these eutectic structures and the maximum circle and minimum circle based on the radius distribution are the actual Si phase (first phase). It can be confirmed that the equivalent circular diameter (average value and diameter distribution) of the second phase almost matches.
  • FIG. 30 (a) shows the silicide (first structure) in the eutectic structure obtained by the above precipitation calculation with respect to the alloy composition of Si 60 Sn 20 Ti 20 in Comparative Example 1 by applying the calculation conditions in Comparative Example 1 above. It is a graph which shows the mode radius of the size of a phase) and Si phase (2nd phase). It can be seen that an independent silicide (first phase) is not formed in the alloy composition of Si 60 Sn 20 Ti 20 in Comparative Example 1. This could also be confirmed by observing the same fine structure as in FIGS. 3 to 8 of Example 2 (not shown).
  • FIG. 30B is a graph obtained by enlarging the graph of FIG.
  • the mode radius of the size of the Si phase (second phase) constituting the eutectic structure is 110 nm.
  • no bimodal distribution was observed for the silicide phase as described above.
  • the peak is the silicide phase (first phase) constituting the eutectic structure, and the mode radius of the size is 180 nm. It is. From the graph of FIG.
  • the radius distribution of the size of the Si phase (second phase) constituting the eutectic structure is 80 to 160 nm.
  • the radius distribution of the size of the silicide phase (first phase) constituting the eutectic structure is 300 to 570 nm.
  • the radius distribution reads a portion having a height of 5% with respect to the peak height.
  • the equivalent circle radius (average value) is 500 nm or less, preferably 450 nm or less, more preferably 400 nm or less, still more preferably 350 nm or less, and particularly preferably 240 nm or less.
  • the lower limit of the equivalent circular radius (average value) of the size of the independent first phase (silicide phase) is not particularly limited, but is preferably 160 nm or more, more preferably 170 nm or more, still more preferably 180 nm or more, particularly Preferably it is 190 nm or more.
  • the equivalent circular radius (average value) of the size of the Si phase (second phase) in 100 eutectic structures on the basis of the number measured from the electron micrographs of FIGS. ) Is less than 110 nm, preferably not more than 100 nm, more preferably not more than 85 nm, still more preferably not more than 70 nm, particularly preferably less than 50 nm, and particularly preferably not more than 48 nm.
  • the lower limit of the equivalent circular radius (average value) of the size of the Si phase (second phase) in the eutectic structure is not particularly limited, but is preferably 25 nm or more, more preferably 30 nm or more, and still more preferably. It is 35 nm or more, particularly preferably 40 nm or more.
  • the equivalent circular radius (average) of the size of the silicide phase (first phase) in 100 eutectic structures on the basis of the number measured from the electron micrographs of FIGS. (Value) is approximately the same size as the equivalent circular radius (average value) of the size of the Si phase (second phase) in the eutectic structure. That is, the equivalent circular radius (average value) of the size of the silicide phase (first phase) in 100 eutectic structures on the basis of the number measured from the electron micrographs of FIGS. 3 to 9 is less than 110 nm.
  • the thickness is preferably 100 nm or less, more preferably 85 nm or less, still more preferably 70 nm or less, particularly preferably less than 50 nm, and particularly preferably 48 nm or less.
  • the lower limit of the equivalent circular radius (average value) of the size of the silicide phase (first phase) in the eutectic structure is not particularly limited, but is preferably 25 nm or more, more preferably 30 nm or more, and still more preferably. It is 35 nm or more, particularly preferably 40 nm or more.
  • the size of the independent first phase and the size of the Si phase (second phase) in the eutectic structure obtained by the precipitation calculation by applying the calculation conditions of Examples 1 to 4 above.
  • the mode diameter and the diameter distribution that is twice the radius distribution are the actual size of the independent first phase in Examples 1 to 4 and the size of the Si phase (second phase) in the eutectic structure. It can be said that it almost agrees.
  • This is equivalent to the equivalent circular diameter (average of 100 independent first phases and Si phases (second phases) in the eutectic structure on the basis of the number measured from the electron micrographs of FIGS. It has been found that the above-mentioned mode radius and radius distribution can be applied without any problem as a new index to replace these equivalent circle diameters.
  • the particle diameter of the silicon-containing alloy constituting the negative electrode active material in the present embodiment is not particularly limited, but the average particle diameter is preferably 0.1 to 20 ⁇ m, more preferably 0.2 to 10 ⁇ m. .
  • the silicon-containing alloy has a second phase in the microstructure. It is configured to be eutectic with one phase and enter a gap between a plurality of independent first phases.
  • a method for producing a negative electrode active material comprising such a silicon-containing alloy, a method for producing a quenched ribbon alloy by a liquid quenched roll solidification method (also simply referred to as a liquid rapid solidification method) is provided as follows.
  • a method for producing a negative electrode active material for an electrical device comprising a silicon-containing alloy having the composition represented by the chemical formula (I), wherein the composition is the same as that of the silicon-containing alloy.
  • a rapidly quenched ribbon alloy is prepared by a liquid quench roll solidification method using a mother alloy having the following composition, and then subjected to a pulverization treatment so as to have the above-mentioned average particle diameter.
  • a method for producing a negative electrode active material for an electrical device is also provided. As described above, by performing the liquid quench roll solidification method to manufacture the negative electrode active material (silicon-containing alloy), it is possible to manufacture the alloy having the above-described microstructure. This provides a production method that can effectively contribute to the improvement of cycle durability while exhibiting a high capacity of the silicon-containing alloy active material.
  • the manufacturing method according to the present embodiment will be described.
  • ⁇ Liquid quenching roll solidification method (preparing process of quenching ribbon (ribbon) alloy)> First, a liquid quench roll solidification method is performed using a mother alloy having the same composition as the desired silicon-containing alloy. Thereby, a rapidly cooled ribbon is produced.
  • a master alloy in order to obtain a master alloy, high-purity raw materials (single ingots, wires, plates, etc.) are used as raw materials for silicon (Si), tin (Sn), and transition metals (for example, titanium (Ti)). Prepare). Subsequently, in consideration of the composition of the silicon-containing alloy (negative electrode active material) to be finally produced, a master alloy in the form of an ingot or the like is produced by a known technique such as an arc melting method.
  • a liquid quench roll solidification method is performed using the mother alloy obtained above.
  • This step is a step of rapidly cooling and solidifying the melt obtained by melting the master alloy obtained above, and is performed by, for example, high-frequency induction melting-liquid quench roll solidification method (double roll or single roll quench method). be able to. Thereby, a rapidly cooled ribbon (ribbon) alloy is obtained.
  • the liquid quench roll solidification method is often used as a method for producing an amorphous alloy, and there are many knowledges about the method itself.
  • the liquid rapid roll coagulation method can be carried out using a commercially available liquid rapid solidification apparatus (for example, a liquid rapid solidification apparatus NEV-A05 type manufactured by Nisshin Giken Co., Ltd.).
  • the gauge pressure in the chamber is desirably adjusted to a range of ⁇ 0.03 to ⁇ 0.07 MPa (0.03 to 0.05 MPa in absolute pressure).
  • the melting temperature of the mother alloy in the melting apparatus may be higher than the melting point of the alloy.
  • conventionally known melting means such as high frequency induction heating can be used.
  • the injection pressure of the mother alloy from the nozzle of a melting apparatus for example, a quartz nozzle
  • an injection nozzle to a range of 0.03 to 0.09 MPa as a gauge pressure.
  • the said injection pressure can be adjusted with a conventionally well-known method.
  • the differential pressure between the chamber internal pressure and the injection pressure is desirably adjusted to a range of 0.06 to 0.16 MPa.
  • the method for obtaining the cooling rate is as described above with reference to FIGS.
  • a microstructure with a mixed eutectic structure of silicide and a-Si phase diffraction patterns (FIG. 10) obtained by fast Fourier transform processing of each part (a plurality of independent primary crystal silicide phases, eutectic a-Si phases, and eutectic silicide phases) in the observed image
  • diffraction patterns (FIG. 11) obtained by X-ray diffraction (XRD) measurement the main component of the crystal structure of disilicide (TiSi 2 ) contained in the quenched ribbon obtained by the liquid rapid solidification method is a C49 structure. It was confirmed to have a C54 structure as an accessory component.
  • C49 structure disilicide (TiSi 2) is a low hardness as compared with disilicide (TiSi 2) of C54 structure. Therefore, when producing a negative electrode active material (silicon-containing alloy) by performing a pulverization process using the quenched ribbon, negative electrode active material particles having a desired size can be obtained without performing a long pulverization process. . Further, as described with reference to FIGS. 10 and 11 described above, by using the C49 structure as a main component and the C54 structure as a subcomponent, the effects of the present invention can be effectively expressed.
  • the properties of the silicide phase having the C49 structure (principal component) and the C54 structure (subcomponent) contained in the quenched ribbon obtained by the liquid rapid solidification method can be effectively used,
  • Such a manufacturing method can be said to be advantageous.
  • the C54 structure (subcomponent) exhibits a lower resistivity (higher electronic conductivity) than the C49 structure, and thus it can be said that the negative electrode active material as a whole has more preferable performance.
  • the above-mentioned silicon-containing alloy having the desired microstructure quenching ribbon (ribbon) alloy It can be produced.
  • a metal or a resin in which a conductive filler is added to a conductive polymer material or a non-conductive polymer material can be employed.
  • examples of the metal include aluminum, nickel, iron, stainless steel, titanium, and copper.
  • a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used.
  • covered on the metal surface may be sufficient.
  • aluminum, stainless steel, copper, and nickel are preferable from the viewpoints of electronic conductivity, battery operating potential, and adhesion of the negative electrode active material by sputtering to the current collector.
  • examples of the conductive polymer material include polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, and polyoxadiazole. Since such a conductive polymer material has sufficient conductivity without adding a conductive filler, it is advantageous in terms of facilitating the manufacturing process or reducing the weight of the current collector.
  • Non-conductive polymer materials include, for example, polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE), etc.), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), polyimide (PI), polyamideimide (PAI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) , Polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF), or polystyrene (PS).
  • PE polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • PI polyimide
  • PAI polyamideimide
  • PA polyamide
  • PTFE polytetraflu
  • a conductive filler may be added to the conductive polymer material or the non-conductive polymer material as necessary.
  • a conductive filler is inevitably necessary to impart conductivity to the resin.
  • the conductive filler can be used without particular limitation as long as it has a conductivity.
  • metals, conductive carbon, etc. are mentioned as a material excellent in electroconductivity, electric potential resistance, or lithium ion barrier
  • the metal is not particularly limited, but at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, Sb, and K, or these metals It is preferable to contain an alloy or metal oxide containing.
  • it includes at least one selected from the group consisting of acetylene black, vulcan, black pearl, carbon nanofiber, ketjen black, carbon nanotube, carbon nanohorn, carbon nanoballoon, and fullerene.
  • the amount of the conductive filler added is not particularly limited as long as it is an amount capable of imparting sufficient conductivity to the current collector, and is generally about 5 to 35% by mass.
  • a liquid electrolyte or a polymer electrolyte can be used as the electrolyte constituting the electrolyte layer 17.
  • the liquid electrolyte has a form in which a lithium salt (electrolyte salt) is dissolved in an organic solvent.
  • organic solvent include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), Examples include carbonates such as methylpropyl carbonate (MPC).
  • Li (CF 3 SO 2) 2 N Li (C 2 F 5 SO 2) 2 N, LiPF 6, LiBF 4, LiAsF 6, LiTaF 6, LiClO 4, LiCF 3 SO 3 , etc.
  • a compound that can be added to the active material layer of the electrode can be employed.
  • polymer electrolytes are classified into gel electrolytes containing an electrolytic solution and intrinsic polymer electrolytes not containing an electrolytic solution.
  • the gel electrolyte has a configuration in which the above liquid electrolyte (electrolytic solution) is injected into a matrix polymer made of an ion conductive polymer.
  • the use of a gel polymer electrolyte as the electrolyte is superior in that the fluidity of the electrolyte is lost and it is easy to block ion conduction between the layers.
  • Examples of the ion conductive polymer used as the matrix polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • electrolyte salts such as lithium salts can be well dissolved.
  • the ratio of the liquid electrolyte (electrolytic solution) in the gel electrolyte is not particularly limited, but is preferably about several mass% to 98 mass% from the viewpoint of ionic conductivity.
  • the gel electrolyte having a large amount of electrolytic solution having a ratio of the electrolytic solution of 70% by mass or more is particularly effective.
  • a separator may be used for the electrolyte layer.
  • the separator include a microporous film made of polyolefin such as polyethylene and polypropylene, a porous flat plate, and a non-woven fabric.
  • the intrinsic polymer electrolyte has a structure in which a supporting salt (lithium salt) is dissolved in the above matrix polymer, and does not contain an organic solvent that is a plasticizer. Therefore, when the electrolyte layer is composed of an intrinsic polymer electrolyte, there is no fear of liquid leakage from the battery, and the reliability of the battery can be improved.
  • a supporting salt lithium salt
  • the matrix polymer of the gel electrolyte or the intrinsic polymer electrolyte can express excellent mechanical strength by forming a crosslinked structure.
  • thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for forming a polymer electrolyte using an appropriate polymerization initiator.
  • a polymerization treatment may be performed.
  • a current collecting plate may be used for the purpose of taking out the current outside the battery.
  • the current collector plate is electrically connected to the current collector and the lead, and is taken out of the laminate sheet that is a battery exterior material.
  • the material constituting the current collector plate is not particularly limited, and a known highly conductive material conventionally used as a current collector plate for a lithium ion secondary battery can be used.
  • a constituent material of the current collector plate for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable, and aluminum is more preferable from the viewpoint of light weight, corrosion resistance, and high conductivity. Copper or the like is preferable. Note that the same material may be used for the positive electrode current collector plate and the negative electrode current collector plate, or different materials may be used.
  • ⁇ Use positive terminal lead and negative terminal lead as required.
  • a terminal lead used in a known lithium ion secondary battery can be used.
  • the part taken out from the battery outer packaging material 29 has a heat insulating property so as not to affect the product (for example, automobile parts, particularly electronic devices) by contacting with peripheral devices or wiring and causing leakage. It is preferable to coat with a heat shrinkable tube or the like.
  • ⁇ Battery exterior material> As the battery exterior material 29, a known metal can case can be used, and a bag-like case using a laminate film containing aluminum that can cover the power generation element can be used.
  • a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used as the laminate film, but the laminate film is not limited thereto.
  • a laminate film is desirable from the viewpoint that it is excellent in high output and cooling performance, and can be suitably used for a battery for large equipment for EV and HEV.
  • the stacked flat lithium ion secondary battery 50 has a rectangular flat shape, and a positive current collector 59 for taking out power from both sides thereof, a negative current collector, and the like.
  • the electric plate 58 is pulled out.
  • the power generation element 57 is wrapped by the battery outer packaging material 52 of the lithium ion secondary battery 50 and the periphery thereof is heat-sealed.
  • the power generation element 57 pulls out the positive electrode current collector plate 59 and the negative electrode current collector plate 58 to the outside. Sealed.
  • the power generation element 57 corresponds to the power generation element 21 of the lithium ion secondary battery (stacked battery) 10 shown in FIG.
  • the power generation element 57 is formed by laminating a plurality of single battery layers (single cells) 19 including a positive electrode (positive electrode active material layer) 13, an electrolyte layer 17, and a negative electrode (negative electrode active material layer) 15.
  • the removal of the positive electrode current collector plate 59 and the negative electrode current collector plate 58 shown in FIG. 2 is not particularly limited.
  • the positive electrode current collector plate 59 and the negative electrode current collector plate 58 may be drawn out from the same side, or the positive electrode current collector plate 59 and the negative electrode current collector plate 58 may be divided into a plurality of parts and taken out from each side. It is not limited to the one shown in FIG.
  • a terminal instead of the current collector plate, for example, a terminal may be formed using a cylindrical can (metal can).
  • the negative electrode and the lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of the present embodiment are large vehicles such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles. It can be suitably used as a capacity power source. That is, it can be suitably used for a vehicle driving power source and an auxiliary power source that require high volume energy density and high volume output density.
  • the lithium ion battery is exemplified as the electric device.
  • the present invention is not limited to this, and can be applied to other types of secondary batteries and further to primary batteries. Moreover, it can be applied not only to batteries but also to capacitors.
  • Si 65 Sn was placed in a quartz nozzle installed in a chamber reduced to a gauge pressure of ⁇ 0.03 MPa after Ar substitution.
  • a mother alloy of 5 Ti 30 was put and melted by high frequency induction heating.
  • lithium hexafluorophosphate lithium salt
  • LiPF 6 LiPF 6 dissolved at a concentration of 1 mol / L was used.
  • Example 3 Except that the alloy type is changed to Si 60 Sn 10 Ti 30 and the chamber pressure in the liquid rapid solidification method is set to ⁇ 0.02 MPa and the injection pressure is set to 0.01 MPa, the negative electrode active A substance, a negative electrode, and a lithium ion secondary battery (coin cell) were produced.
  • the first phase mainly composed of a silicide of Ti element (silicide) as a transition metal and partly tin (Sn)
  • a second phase mainly composed of amorphous or low crystalline Si, a part of which is a plurality of independent first phases, and a part of
  • the first phase and the second phase have a eutectic structure (not shown).
  • the Sn phase is crystallized in the outer part of the first phase and the second phase (not shown).
  • the size of the independent first phase and the Si phase (second phase) in the eutectic structure in the microstructure of the negative electrode active material (silicon-containing alloy) produced in Examples 1 to 4 and Comparative Example 1 The size is as described above with reference to FIGS. Specifically, for the alloy compositions of Examples 1 to 4 and Comparative Example 1, the size of the independent first phase obtained by the above precipitation calculation using the calculation conditions of Examples 1 to 4 and Comparative Example 1 above and The results of the mode radius and radius distribution of the size of the Si phase (second phase) in the eutectic structure are shown in Table 1 below.
  • the evaluation cell is in a constant current / constant voltage mode in the charging process (referring to the Li insertion process to the evaluation electrode) in a thermostat set to the above evaluation temperature using a charge / discharge tester.
  • the battery was charged from 2 V to 10 mV at 0.1 mA.
  • a constant current mode was set and discharge was performed from 0.3 C, 10 mV to 2 V.
  • the charge / discharge test was conducted from the initial cycle (1 cycle) to 50 cycles under the same charge / discharge conditions with the above charge / discharge cycle as one cycle.
  • the results of determining the ratio of the discharge capacity at the 50th cycle to the discharge capacity at the first cycle are shown in Table 1 below.
  • the lithium ion batteries using the negative electrode active materials of Examples 1 to 4 have a high discharge capacity retention rate after 50 cycles and are excellent in cycle durability. I understand that. Further, in Examples 1 to 4 using the Si alloy negative electrode, the capacity is higher than that of the negative electrode active material using the carbon material (this point is not limited to showing a comparative example using the carbon material. Since it is publicly known (see Background Art), the comparative example is omitted). The reason why high cycle durability was achieved while exhibiting such a high capacity was that the Si-containing alloy constituting the negative electrode active material was Si-Sn-M (M is one or more transition metal elements). By having the ternary alloy composition represented.
  • the microstructure has a first phase mainly composed of silicide and a second phase partially including Sn and mainly composed of amorphous or low crystalline Si. This is because a plurality of independent first phases and partly a first phase and a second phase have a eutectic structure.
  • the lithium ion battery using the negative electrode active material of Comparative Example 1 does not have sufficient cycle durability. This is because the independent first phase is not formed in the negative electrode active material of Comparative Example 1 as shown in Table 1.
  • the eutectic first phase can suppress the expansion of the second phase (Si phase) in the eutectic structure in the charge / discharge process to some extent, a plurality of independent first phases ( This is probably because it cannot be suppressed by a two-stage suppression.
  • the degree of expansion of each refined Si phase can be relatively reduced by reducing (miniaturizing) the size (mode radius) of the Si phase that expands and contracts during the charge / discharge process. That is, it is possible to reduce the expansion pressure (stress / load for pressing the surrounding silicide) when the individual refined Si phase expands. For this reason, the eutectic first phase can easily suppress the expansion of the second phase (Si phase) (reduction pressure due to reduction; stress / load that compresses the reduced surrounding silicide). Further, the expansion of the reduced Si phase in the eutectic structure formed in the gaps between the plurality of independent first phases that have become smaller is more easily suppressed by the independent first phase that surrounds the gaps.
  • Lithium ion secondary battery (stacked battery), 11 negative electrode current collector, 12 positive electrode current collector, 13 negative electrode active material layer, 15 positive electrode active material layer, 17 electrolyte layer, 19 cell layer, 21, 57 power generation element, 25, 58 negative electrode current collector plate, 27, 59 positive current collector, 29, 52 Battery exterior material (laminate film).

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Abstract

Le problème décrit par l'invention est de pourvoir à un moyen qui permette d'améliorer la durabilité en cycles d'un dispositif électrique tel qu'une pile rechargeable lithium-ion. La solution de l'invention consiste à utiliser, dans un dispositif électrique, un matériau actif d'électrode négative qui comprend un alliage contenant du silicium ayant une composition d'alliage ternaire représentée par Si−Sn−M (M étant un ou plusieurs éléments métaux de transition). L'alliage contenant du silicium présente une structure dont la microstructure comprend une première phase, qui contient un siliciure d'un métal de transition comme constituant principal, et une seconde phase, qui contient partiellement du Sn et contient du Si amorphe ou faiblement cristallin comme constituant principal, et une partie de la structure comprend une pluralité de premières phases indépendantes et une partie de la structure comprend une structure eutectique de la première phase et de la seconde phase.
PCT/JP2015/081662 2015-11-10 2015-11-10 Matériau actif d'électrode négative pour dispositif électrique, et dispositif électrique utilisant ledit matériau Ceased WO2017081758A1 (fr)

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MYPI2018000669A MY173412A (en) 2015-11-10 2015-11-10 Negative electrode active material for electric device and electric device using the same
CN201580084375.3A CN108352513B (zh) 2015-11-10 2015-11-10 电气设备用负极活性物质和使用了其的电气设备
US15/774,920 US10403890B2 (en) 2015-11-10 2015-11-10 Negative electrode active material for electric device and electric device using the same
KR1020187012641A KR20180061348A (ko) 2015-11-10 2015-11-10 전기 디바이스용 부극 활물질, 및 이것을 사용한 전기 디바이스
EP15908282.5A EP3376570B1 (fr) 2015-11-10 2015-11-10 Matériau actif d'électrode négative pour dispositif électrique, et dispositif électrique utilisant ledit matériau
PCT/JP2015/081662 WO2017081758A1 (fr) 2015-11-10 2015-11-10 Matériau actif d'électrode négative pour dispositif électrique, et dispositif électrique utilisant ledit matériau
JP2017549910A JP6583426B2 (ja) 2015-11-10 2015-11-10 電気デバイス用負極活物質、およびこれを用いた電気デバイス

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DE202017007716U1 (de) * 2016-06-14 2025-01-22 Nexeon Limited Elektroden für Metall-Ionen-Batterien
CN111146409B (zh) * 2018-11-05 2021-02-26 宁德时代新能源科技股份有限公司 负极活性材料、其制备方法及二次电池
EP3763845B1 (fr) * 2019-07-08 2021-08-18 LKR Leichtmetallkompetenzzentrum Ranshofen GmbH Alliage de magnesium et son procédé de fabrication
KR102871360B1 (ko) * 2019-11-11 2025-10-15 삼성에스디아이 주식회사 전고체 이차전지

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US10403890B2 (en) 2019-09-03
US20180351170A1 (en) 2018-12-06
JPWO2017081758A1 (ja) 2018-06-21
EP3376570A4 (fr) 2018-09-19
CN108352513B (zh) 2019-10-01
EP3376570A1 (fr) 2018-09-19
EP3376570B1 (fr) 2020-03-11

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